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By N. S. Stoloff, R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-Co and Fe- V alloys containing up to 25 pct solute have been studied in the temperature range 25° to - 196°C. The microyield stress is independent of temperature for all alloys studied, while the temperature dependence of the ordinary yield stress is large and comparable to that for unalloyed iron. An alloy-softening phenomenon is observed for many alloys relative to unalloyed iron, and appears to be a consequence of removal of inter-stitials from solution and their subsequent agglomeration. The ductile to brittle transition temperature is increased markedly by both cobalt and vanadium. Transmission electron microscopy observations reveal that cross slip and cell formation are restricted with increasing solute, which can account for many aspects of yielding and fracture behavior. IRON and other metals of bcc structure slip on many planes of the (111) zone at moderate and elevated temperatures, giving rise to wavy glide. At low temperatures, however, there is a tendency for slip to be restricted to planes of only one or two crystallographic types; in the case of Fe-Si alloys for example, (110) glide predominates, giving rise to planar slip bands."' Restriction of cross slip at low temperatures in iron has been linked by Brown and Ekvall3 to increased strain hardening in the preyield microstrain region, leading to an apparently large temperature dependence of the yield stress. Support for this view has been provided by Lawley and Gaigher4 from a transmission electron microscope study of molybdenum. They concluded that dislocations at lower temperatures, by virtue of their inability to change planes readily, are unable to interact and annihilate, leading to an increase in internal stress and work-hardening capacity. Restriction of cross slip at low temperatures has also been suggested to be an important factor in determining the ductile to brittle transition of single-phase solids, including metals of bcc structure.5 It is pertinent to note that most solute elements tend to raise the ductile to brittle transition temperature of poly crystalline ferrite,6,7 although in some cases, e.g., Fe-Cr7 and Fe-Al,8 the dilute alloys may actually yield at lower stresses than unalloyed iron. It appears, therefore, that solute elements may have an effect analogous to lowering the test temperature with regard to restricting cross glide. Such an effect has indeed been observed in the ionic alloy system KCl-KBr,9 in which bromine atoms, although causing little misfit and consequently little effect on the yield stress of KC1, have a pronounced effect in restricting wavy glide and inducing brittleness. The purpose of the present investigation was to determine the effects of selected solute atoms on the yield stress and fracture behavior of iron, and to elucidate in turn how the slip character was related to these properties. Since it is known that interstitial atoms exert a strong influence on the mechanical behavior of iron, the solute elements chosen for study were vanadium, which reacts strong with interstitials,10 and cobalt, which does not form highly stable interstitial compounds." EXPERIMENTAL PROCEDURE Four-pound ingots of each of the following alloys were vacuum-melted in zirconia crucibles: Fe-1, 5, 10, 25 at. pct Co, and Fe-1, 4, 10, 20 at. pct V. An ingot of unalloyed iron from the same original stock as that used for the alloy was remelted under similar conditions to eliminate variations in interstitial content arising from differing thermal histories. Chemical analyses of the iron, cobalt, and vanadium melt stock are listed in Table I. All ingots were rolled and swaged, commencing at 850°C, to 1/4-in.-diameter bar. The bars were then annealed at 850°C for 1 hr (except that the 10 and 20 pct V alloys were heated for 2 hr) to give a uniform equiaxed grain size of about 0.05 mm. Tensile samples of 0.125 in. diameter by 0.8 in. gage length were utilized for studies of the ductile to brittle transition. A second set of tensile samples were utilized for microstrain experiments in which strain sensitivity of 1 x 10"6 was achieved by a capacitance method.3 Cylindrical compression samples 0.250 in. diameter by 0.4 in. long also were prepared to study the influence of composition on the macroscopic yield stress, and for metallographic analyses of defor-

Jan 1, 1965

By R. D. West

Miscible displacenzent recovers all oil in the area contacted by the injected .fluid, whereas water or immiscible gas drives usually leave substantial amounts of oil as residual. However, the Door mobility ratios associated with a gas-driven miscible displacement cause the sweep pattern efficiency to be much lower than that obtained with water flooding. One way in which the sweep eficiency in a miscible displacement process can be increased is by decreasing the mobility behind the flooding front. This can be achieved by injecting water along with the gas which drives the miscible slug. This water reduces the relative permeability to gas in this area and thus lowers the total mobility. The main operating conditions for the simultaneous injection -vrocess are that a zone of gas exists between the miscible slug and the leading edge of the water and that a su,@cient amount of gas be injected with the water to form the pas volume which is being left in the water zone. Laboratory model studies have shown that the ultimate sweep pattern efficiency can be as high as 90 per cent for a five-spot flooding system. If gar alone is used as the driving medium an ultimate sweep-out efficiency of about 60 per cent would be obtained in the same system. I INTRODUCTION The miscible displacement processes are a step towards total oil recovery. Conventional gas or water drives usually leave 25 to 5.0 per cent of the oil as residual in the swept portion of the reservoir. This residual can be eliminated if the oil is driven by a fluid with which it is miscible. At some reservoir conditions natural gas will become miscible with the oil. This is the "high pressure gas process".' More often, the oil does not contain enough light hydrocarbons to cause the gas to become miscible with the oil at reasonable pressures. In these cases a small band of fluid which is miscible both with the oil and gas must be kept between them2. Less than 2 per cent of the reservoir volume of the slug material is needed to keep the displacement miscible. Both processes work in the same manner, recovering all of the oil in the portion of the reservoir contacted by the injected fluids. The only difference is the manner in which the miscibility between the oil and the injected gas is obtained. Previous publications have contained detailed descriptions of these processes.1,2,3,4 However, total displacement of the oil in the swept region does not guarantee an efficient recovery process. The amount of oil to be recovered is also determined by the fraction of the reservoir contacted by the flood. This fraction is largely determined by the mobilities of the fluids. (The fluid mobility is the permeability of the rock to that fluid divided by the fluid's viscosity, k/p). This. dependence of the fraction swept on the mobility ratio has been shown in previous studies. Fig. 1 shows the ultimate fraction swept in a five-spot system as a function of the mobility ratio. The small drawings show the location of the areas left unswept for two different mobility ratios. The ultimate fraction of the reservoir swept is here considered to be attained when the producing stream contains less than 5 per cent oil at reservoir conditions. THE GAS-DRIVEN MISCIBLE DISPLACEMENT Since there is no oil left in the swept region after miscible displacement the mobility in this region is very high. It is often 50 times the mobility in the unswept regions. This means that the fraction of the reservoir contacted by the injected fluid will be less for a gas-driven miscible displacement than for a conventional water or gas drive. For a five-spot injection system, water would contact the entire reservoir volume, and the low pressure gas would contact about 90 per cent of this volume, while a gas-driven miscible displacement would only contact about 65 per cent of the reservoir. This poor sweep efficiency often offsets the benefits obtained through miscible displacement. Fig. 2 shows what the recovery curves for the three processes might look like for a five-spot system. The curves show the fraction of the in-place oil recovered as a function of reser-

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.' Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.' STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By M. M. Rao, P. G. Winchell

The growth rates of bainitic plates were measured at 400°C in Fe-Ni-C alloys containing 0.10 atom-fract~on nickel and 0.0012 to 0.0075 atonz-fraction carbon. The growth rates are adequately represented by where xc is nearly the atom fraction carbon of the bulk austenite and PXCy is nearly the carbon atom fractlon in the ferrlte of radiids p In equilibrium with austetzite. The form of the equation is that predicted by a model in which carbon diffusion in austernite controls the gvowth, but the numerical constatnt is two orders of magnitude below that suggested by the model. THE growth of bainitic plates in steel is often assumed to be controlled by the diffusion of carbon away from the advancing plate tip. This hypothesis predicts that the growth rate will increase as the carbon content of the austenite, xCz, is reduced toward the carbon content of the saturated ferrite comprising the plate tip, PxCY The growth rate should vary approximately as (xCg- pxCy)-1. Experimental observation of the growth behavior at low carbon levels should provide a significant test of this model. An alloying element in addition to carbon is required so that low-carbon austenite can be experimentally observed while undergoing bainitic transformation. Nickel was selected. The presence of nickel complicates the interpretation of the data in two ways: First, diffusion of nickel during the transformation would make analysis very difficult. Nickel is assumed immobile during the transformation. Second, nickel affects the solubility of carbon in ferrite and austenite in equilibrium. This effect has been evaluated.' At the completion of our experimental work Goode-now et al.2 published data in essential agreement with the observations to be reported here. Since their discussion is abbreviated and their data are scanty in the region of interest, we believe the present work is of significance. I) THE MODEL OF BAINITIC PLATE GROWTH The rate of lengthening of a plate is assumed to be controlled by the diffusion of carbon from the advancing ferrite-austenite interface into the surrounding austenite. The precipitation of carbides is assumed to be a secondary process. For ease of analysis the carbon-atom ratio,* pxCy, of austenite in equilibrium with ferrite which is convex with minimum curvature radius p, and the carbon-atom ratio, PxCY, of that ferrite in equilibrium with austenite are assumed independent of location on the ferrite-austenite interface. Since these carbon contents vary with the radius of curvature of the ferrite, p, their assumed positional independence must be held as an approximation. The consequences of these assumptions have been developed approximately by zener3 and Hillert,4 and the resulting equation for a platelet has been applied to bainite by Speich and cohen5 and Kaufman, Radcliffe, and Cohen.8 The Zener-Hillert equation* for plates is: The analysis of Hillert is supported by that of Hor-vay and cahn7 which involves no mathematical approximations but does include the assumption that the a/y interface coincides with an isoconcentration line. The solutions of Horvay and Cahn for elliptic paraboloids are replotted in Fig. 1. The shape of the paraboloid is expressed in terms of the ratio of the principal radii of curvature at its tip, A =p1/p2, which is also the ratio of the minor to the major axis of the elliptic cross section. The Zener-Hillert equation for plates is also plotted. The agreement is within a factor of two for (pxyaCr - xyC )/(xyC - PxCaY) between 0.5 and 100. This is the range of interest here and in most other work on bainite. The original form of the Zener-Hillert equation was the form given above with the right-hand side replaced by (pxCya -xCy)/(PxCya). This replacement is not appropriate here. 11) THE EXPERIMENTAL PROCEDURE Alloys were prepared and three kinds of experiments carried out. Continuous-cooling-transformation experiments were carried out on wires by measuring temperature and resistance during continuous cooling. Isothermal-transformation experiments were carried out on wires by measuring electrical resistance as a

Jan 1, 1968

By J. L. Huitt, J. L. Pekarek, D. K. Lowe

In a theoretical study of hydraulic jetting, the velocity of the abrasive material relative to the velocity of the fluid in the jet stream is analyzed as the jet stream moves through the convergent and straight sections of the nozzle and the region between the nozzle exit and target. The results revealed that the abrasive material exits from the jet nozzle at a lower velocity than the fluid. The exit pmticle velocity can be increased by increasing either the density of the fluid or the length of the nozzle, and/ or decreasing either the particle density or particle diameter. In the divergent jet stream, there exists a point after which the particle velocity exceeds that of the fluid. The relative velocities were considered in the derivation of an equation to predict cutting rate of a circumferential notch and maximum notch depth. Data of a general nature and data which substantiate the theoretical results were obtained experimentally. INTRODUCTION The use of a fluid containing an abrasive material has been an established technique for cleaning and cutting for many years. In the petroleum industry, the early effort to use this technique1 to perforate and/or to overcome wellbore damage met with only limited acceptance because of the short life of the jet nozzle. With the introduction of improved perforating techniques, and later, hydraulic fracturing, the use of hydraulic jetting as a well completion technique became even less appreciated. It was only in recent years that interest in hydraulic jetting was revived. Once this interest was revived, the results of surface tests stimulated the interest of the industry even more than the state of the technology probably warranted because many of the tests were not appropriate for down-hole conditions. However, because of the stimulated interest, the development of the jet nozzle progressed very rapidly to the point where the nozzle life was no longer a prob- lem. With this accomplished, the use of hydraulic jetting in well completion became an accepted practice in a short time. The purpose of this paper is to present a theoretical analysis of the hydraulic jet stream as it passes through the nozzle and travels to its target. With a better understanding of the jet stream and the effects of various parameters, the performance of the process can be predicted more accurately. Equations are presented for cutting rate as applied to circumferential wellbore notching that relate the jet stream make-up, notch configuration and formation material. Also, experimental data are presented on some factors pertinent to hydraulic notching that are not theoretically analyzed. RELATED STUDIES Most of the studiesl-5 reported in the recent literature have pertained to the more practical aspects of hydraulic jetting; i.e., the effects of certain parameters as interpreted from experimental results, and the application of hydraulic jetting in well completion. In reviewing the effects of various parameters, it is interesting to note the reported depths of penetration obtained under various imposed conditions. In general, the depths vary from a few inches to several feet; however, a depth of penetration of less than 6 in., as reported by Thompson,4 seems more realistic for the usual field practice of hydraulic jetting with sand in water for a period of 20 to 30 minutes. In addition to the practical aspects, the study of Brown and Loper5 included a theoretical approach to hydraulic jetting. Their study resulted in the development of a theoretical expression for the maximum depth of penetration if jetting were continued for an infinite time. An analysis of the equations presented reveals that the initial cutting rate is infinite. The equation expressing centerline velocity is that of Forstall and Gaylord,6 which is applicable for a jet stream exiting in a large stationary medium. Since practically all of the fluid pumped into a perforation (or cut) must flow back through the perforation prior to re-entering the wellbore, a description of the medium as finite and non-stationary seems more reasonable. Thus, in this

By J. A. Coll, R. W. Cahn, A. Lawley

WHILE the creep properties of pure face-centered-cubic and close-packed-hexagonal metals have been thoroughly investigated and are well established, body-centered-cubic metals have been studied less extensively. Moreover, very few fundamental studies on the creep of solid solutions, irrespective of crystal structure, have been reported. The present study is concerned with the creep of a series of body-centered-cubic solid solutions. The present position concerning creep of pure metals is, briefly, as follows.1"3 Creep at first takes place at a steadily decreasing rate; this is the stage termed primary or transient creep. Except at the lowest temperatures this is succeeded by a stage of secondary or steady-state creep. At high temperatures and stresses, this may be succeeded by an accelerating stage, termed tertiary creep, with which we shall not here be concerned. There is no well-defined physical model at present for the transient stage; in general terms, transient creep is best regarded simply as a manifestation of work-harden ing. Steady-stage creep can certainly take place by several different mechanisms: the choice of dominant mechanism depends primarily on temperature. We shall here be concerned only with high-temperature steady-state creep, a term usually reserved for creep at absolute temperatures higher than 0.5 Tm, where T, is the melting point. In this range, the activation energy for creep is, for many metals, equal to the activation energy for self-diffusion, and this is generally interpreted in terms of a "climb mechanism.1-4 The creep rate is determined by the speed at which dislocations, impeded by obstacles the nature of which is disputed but which are probably established during transient creep, can climb by means of a diffusion process, until they are able to by-pass the obstacle. In solid solutions, the intrinsic resistance to the slip motion of dislocations may be much larger than in the solvent, to the extent that the motion of dislocations in the glide plane, rather than their escape by climb out of this plane, may become the rate-controlling factor. weertman5 has considered this possibility from a theoretical point of view, and concluded that some form of "viscous slip" is likely to be rate-controlling at comparatively low stresses. The resistance to slip may arise from "atmospheres" of impurities forming around dislocations; a high Peierls force in materials of high cohesion; or some structural peculiarity such as clustering or ordering of solute atoms.= We shall be concerned here with the case of ordering. The only published investigations concerned explicitly with the effect of order on creep refer to creep in ß-brass by Herman and Brown,7 and in Ni-Fe alloys, by Kornilov and panasyuk8 and by Suzuki and Yamamoto.9 Recently, Herman and Brown's paper has been supplemented by a determination of the tensile yield point of ß-brass as a function of temperature.10 Both studies showed a sharp drop in resistance to deformation of ß-brass over a range of a few degrees just above the critical temperature Tc at which order finally disappears. These observations are especially noteworthy, because in ß brass the degree of order diminishes steadzly to zero as the temperature approaches Tc. It is, therefore, the disappearance of the last traces of long-range order which has the largest effect on the resistance of the alloy to plastic deformation. In the Ni/Fe alloys of various compositions, resistance to creep at a given temperature and stress is maximum at the stoichiometric composition, both below Tc, (long-range order), and above T,. (short-range order).' Near Tc, the creep resistance of an ordered alloy is much higher than that of the same alloy in the disordered condition.9 The aim of the present investigation was to study the creep behavior in the neighborhood of Tc, of another system of ordering alloys. The iron-aluminum alloys were considered the most suitable. because: i) The order again diminishes steadily to zero as the temperature approaches Tc; there is no sudden drop in order at Tc, and it therefore is

Jan 1, 1961

By R. H. Edsal, G. Horvay

The transient one-dimensional heat-conduction equation is solved for two semi-infinite media, at different initial temperatures, brought into (poor) thermal contact. It is shown that the two interface temperatures gradually approach the well-known, instantaneously assumed, common interface temperature of the case of zero contact resistance. The present analysis, with slight modifications, may be used in fair approximation also for the class of problems involving a change of phase. One particular application of the boundary value problem solved in this paper concerns the determination of the temerature distribution in metal castings and molds.P This problem has been treated extensively by analytical methods (see e.g., the literature listed in Refs. 1 to 4) by electrical analogs (see e.g., Refs. 11 to 14) and also by experimental methods (see the literature listed in Refs. 4, 5), but prior to the work of Pellini and Ruddle the experimental results were rather unreliable. Immediate motivation for the work described in this paper was to better understand the results of Pellini,' which are typified by the curves of Fig. 1. Pellini cast 20-in. high, 7-in. sq steel ingots into cast-iron molds of various thicknesses. He measured the temperatures at mid-height, at a number of stations in the casting and the mold, and obtained the cooling curves shown in Fig. 1. The most conspicuous thing about Fig. 1 is the large temperature discontinuity at the interface between casting and mold, due presumably to the shrinking away of the casting from the wall and the attendant creation of an airgap, as the casting cools. Such a contact resistance slows down the anticipated freezing rate; an analytical prediction of this is of much interest in foundry practice. The determination of the effect of contact resistance in the presence of a change of phase will be dealt with, by an approximate method, in a separate paper.' In the present paper the much simpler problem is considered in which there is contact resistance but no change of phase. This problem frequently arises in the analysis of aircraft structures.+ It can initial temperature, and may be regarded as semi-infinite. We suppose the thermal properties in the two media to be time, temperature, and space independent; there are no sources or sinks within the media. In Fig. 2(a) we illustrate, schematically, the case of no contact resistance. The semi-infinite media "0" and "2:' initially at temperatures 8 (- m) and 8(+ -), respectively, are brought into contact at time t =0. A common interface temperature 8,i = is instantaneously established, and thereafter remains constant. Temperature curves are drawn for three instants of time. When there is contact resistance between the two media, the temperature equalization occurs as sketched in Fig. 2(b). Fig. 2(c) illustrates a temperature curve, using the dimension-less notation Barber-Weiner-Boley6 have stated the equations [23a, b] given below, which govern the heat transfer in the two media, and solved them for a rather complicated special case. In their example both media "O" and "2" are finite, are insulated at their far ends, and there is steady heat input into medium 2. In Eq. [27] we give the general solution of the most important special case, where the two media are semi-infinite and there are no sources or sinks. In this case the results may be stated in simple closed form. In Fig. 3, to be discussed in the next section, we illustrate the variation of the interface temperature when steel at 2760" is brought into contact with iron at 100". This example, if we disregard the effect of the heat of fusion, is comparable to Pellini's experimental results, Fig. 1. (Unfortunately, however, experimental determination of the interface temperatures was difficult to carry out, and hence Fig. 1 is not very accurate near the interface.) In Figs. 4 and 5 of the following section, we similarly compare Pellini's sandcasting tests with analytical results for the case where steel at 2760" is brought into contact with sand at 100". It will be pointed out that, insofar as the interface temperatures are concerned, heat of fusion has a minor effect, and so the present approximation, with small modifications, may be

Jan 1, 1961

By A. G. Guy

Thermodynamic activity rather than chemical composition is basic to the analysis of diffusion. This is the essential conclusion reached by Darken1-3 and by Birchenall and Mehl.4 If so, it is reasonable to expect that diffusion calculations should be carried out using activities. This paper will illustrate a method of employing activities in analyzing interstitial diffusion. For interstitial diffusion (of carbon in iron and probably generally) the diffusion of the solvent atoms, volume changes, and other such complexities not explicitly provided for in the usual diffusion equations cause a negligible error of the order of 1 pct. Therefore it is relatively easy to test the validity of an analysis based on activities in the instance of interstitial diffusion. The mathematical treatment of the more complex substitutional diffusion could be simplified once the adequacy of the activity method had been established for substitutional diffusion. Thus the present work has the purpose not only of providing a superior analysis of interstitial diffusion but also of indicating a possible approach to the more important question of an adequate treatment of substitutional diffusion. Development of the Diffusion Equation Although activities are convenient quantities to determine experimentally, they are derived from the more fundamental fugacities.9 Possible confusion in using activities can be avoided by basing equations involving their use on the relationship, dP = -D1d/ax dt [I] where, dP = the number of grams of solute crossing one cm2 in the time dt sec. D, = the diffusion constant for use with fugacities; it is assumed to be constant at a given temperature, and has units of secs. f = the fugacity of the solute in the solid solution; the units are those of pressure, dynes per cm2. x = the distance in cm. Eq 1 can be considered to be the basic form of the first Fick Law for one-dimensional diffusion. In order to convert Eq 1 into an equation involving activities, a choice of a standard or reference fugacity, f°, must be made: then. a = f [2] where a is the activity corresponding to the fugacity f. However, the value of a is also determined by the relation, a = a\c [3] where a is the activity coefficient and c is the concentration. For a given value of a (such as a = 1) it is evident that the units used for expressing concentration will affect the numerical value of a corresponding to a given amount of carbon dissolved in y-iron. Since weight per cent concentration is so widely used, this unit will be adopted as the standard in this paper. When the value off given by Eq 2 is substituted in Eq 1, the first Fick Law becomes, dP= -D,f°dl [4] Since D,f° is constant (at a given temperature), the second form of Fick's Law can be obtained in the usual manner, -dt D'f° dx [5] where c' is the concentration in g per cm3. In terms of weight per cent concentration, c, Eq 5 becomes, dc _ 100 d2a Tt = T /f w [6] where p is the density of the solid solution and will be assumed to be constant. In order to simplify Eq6, it is necessary to consider the standard state, f°. Standard states are chosen for convenience. There appears to be one especially convenient choice for the analysis of interstitial diffusion. If the activity coefficient, a, is set equal to unity at infinite dilution of the solute, 100 then — 100D1fl° is approximately equal P to the usual diffusion constant in dilute solutions. This is true since the activity, a, in Eq 6 can be replaced by the concentration, c, with little error in an infinitely dilute solution.* Here f1° is the standard fugacity necessary to achieve this standard state. It is proposed that a diffusion constant Da' be defined, Da1=100/pD1f1° [7] where A is the metal whose diffusion is * The second derivative of a is equal to the second derivative of c in dilute solution only if -da/dr- is. zero. Although theory does not require this condition, in the systems C in Fe, and Zn in Cu, dc is in fact found to be essentially zero.

Jan 1, 1950

By C. W. Mueller, P. H. Robinson

A technique was developed for depositing single -crystal films of silicon on single-crystal sapphire substrates via the pyrolytic decomposition of SiH4/H2 mixtures. Electron diffraction and X-ray Laue reflection examinations of these films revealed single-crystal patterns. These films were characterized by measuring conductivity type, thickness, resistivity, and Hall mobility. Chemical etching, dislocation staining, and electron-microscopy examination have indicated the presence of low-angle grain boundaries and microtwinning in the silicon films. The role of the sapphire substrate with respect to its quality, orientation, surface finish, and thermal and chemical treatment was investigated. Hall mobility as a function of sapphire orientation was measured. A mobility equal to 88 pct of bulk silicon mobility was attained. Insulated-gate field-effect transistors which have a transconductance of 4000 pmho at 6 ma were fabricated using these films. THE technology of the fabrication of microelectronic circuits with active and passive components directly on a single wafer of semiconductor material has attained a high degree of perfection during the last few years. One inherent difficulty with the single-wafer approach has been undesirable coupling between components arising from the common base material. Several techniques have been developed for minimizing this coupling and obtaining good electrical isolation between components; however, these result in extra capacitance being added to the circuit. The extraneous capacitance of the connecting leads, resistors, and capacitors degrade circuit performance and limit the high-frequency operation of these circuits. Recently there has been considerable interestl-3 in the deposition of silicon films upon insulating substrates. The use of silicon as the semiconductor allows the subsequent utilization of the large amount of technology which has been developed for silicon for the fabrication of good active components. A sapphire substrate supplies an excellent insulating material which at the same time gives a thermal-conductivity improvement of an order of magnitude over glass-type substrates. This paper will describe the results obtained for the deposition of single-crystal silicon layers upon single-crystal sapphire substrates as well as the characterization of these films. I) APPARATUS The 'system used for the growth of silicon films on sapphire substrates by means of the pyrolysis of SiH4/H2 mixtures is shown in Fig. 1. The all-quartz reaction chamber is water-cooled and includes a quartz optical-flat window for use in conjunction with a 5 kw, 2.5 Mc per sec constant-temperature controlled rf generator. The temperature sensor for the rf generator is a thermopile which is focused through the quartz optical flat onto the susceptor surface. With this system the rf generator will hold the temperature of the susceptor to about +0.3°C at 1200°C. The susceptor is supported on a quartz sled inclined to the gas flow to increase the uniformity of the deposition. The water jacket surrounding the reaction chamber is used to keep the quartz wall temperature low enough to limit the decomposition of the silane to the rf-heated susceptor which contains the sapphire substrates. This eliminates the reaction of silicon with the hot quartz to form SiO which deposits out on the apparatus walls, thus obscuring vision, and interferes with the optical measurements of the temperature as well as with the growth process itself. Provision is also made for "n"- and 'p"-type doping by using mixtures of either phosphine or diborane in hydrogen which are added to the silane during the growth process. The hydrogen used is the purest commercially available tank hydrogen further purified by use of a palladium diffuser. The susceptors which were used include 1) spectro-scopically pure graphite, 2) high-purity molybdenum, 3) high-resistivity silicon using a low-resistivity insert to facilitate coupling to the rf generator, 4) silicon carbide-coated graphite. The latter two susceptor materials produced silicon films on sapphire substrates with more reproducible resistivities. Prior to silicon deposition all connecting lines as well as the reaction chamber are thoroughly flushed with argon and then hydrogen. After the hydrogen flow is set, the growth temperature is adjusted to 11009 to 1150°C, and when thermal equilibrium is reached the silane flow is started. The flow rate of the hydrogen must be fast enough so that turbulent flow occurs in the size of reaction tube used, otherwise a streaked nonuniform silicon deposit occurs. After the deposition

Jan 1, 1967

By Strathmore R. B. Cooke, Paul B. Queneau

The kinetics of the dissolution of scheelite in basic solutions of carbonate and fluoride were investigated. Work was also done with solutions of alkali metal chloride, hydroxide, phosphate, and mixtures of phosphate and fluoride. The study was conducted at 90 psig and at temperatures ranging from 100" to 155"C, and both natural and synthetic scheelite single crystals were used. The interaction of scheelite with carbonate solutions generally followed a parabolic rate law, and resulted in the formation of calcite crystals on the attached surface. The transport of the CO3 through the calcite to the scheelite surface was probably rate -controlling between 115" and 135°C. Positive deviations from Parabolic behavior were observed at 100" and 155?C, presumably due to the calcite grain growth, and to the formation of a noncoherent calcite layer, respectively. The leaching of scheelite with alkaline fluoride solution produced a calcium fluoride reaction-product which covered the surface as a sheet-like layer. Below 110°C the dissolution rate was parabolic; at 115" and 135°C it was linear. In the linear region, the periphery of the calcium fluoride layer lifted from the sample. Only the lower layers, braced by the scheelite substratum, remained unbroken. This bound layer, approximately constant in thickness, limited the rate at which the fluoride could attack the scheelite. The phosphate and phosphate-fluoride leaches dissolved scheelite at a linear rate; solid reaction products were respectively hydroxyapatite and fluorapatite. Sodium hydroxide and chloride were not effective leachants, and did not produce observable solid reaction products. THE feasibility of pressure leaching of scheelite pulps with basic solutions containing either carbonate or fluoride ions, as indicated by the following equations, has been established by previous investigators:1-3 200°C CaWO4s + CO37q - CaCO3s+WO4aq [1] 200°C CaWO4s + 2Faq ^ CaF2s+WO4aq [2] It is to be noted that a commercial process employing reaction [I] is in use at Union Carbide's operation near Bishop, Calif. In the earlier work referred to, it was apparent that the precipitation of the solid reaction-product on the scheelite particles sharply reduced contact of the leachant with the scheelite. We have extended this work by studying the kinetics of dissolution employing single crystals of scheelite of known exposed surface area. In addition, the effectiveness of solutions of phosphate, of phosphate with fluoride, and of chloride and hydroxide as leachants for scheelite have been investigated. EXPERIMENTAL Apparatus. The low-pressure autoclave used in this wo (100 psig maximum) is essentially that of J. Halpern4 as modified by F. A. Forward.5 Constructed entirely of 316 stainless steel, its maximum capacity is 4000 ml. The temperature in the autoclave was regulated to *0.5?C by a Wheelco thermocouple controller. A 4-in. diam, three-bladed impeller, circulated solution upward against the sample, and a strobo-scope permitted holding the stirring rate to *15 rpm. A check valve and a "pop" type safety valve were installed, a sample holder was fixed to an externally adjustable rod, and a water-cooled condenser was placed in series with the sampling valve. The stainless steel sample holder, Fig. 1, held the epoxy-mounted sample (f) five mm above the impeller. Tightening the tapered sleeve (d) positioned the epoxy-resin specimen-mount by forcing it back against the spacer (c). The mount (e) was 1 in. diam. Sample Description and Preparation. Both synthetic and natural scheelite crystals were leached. The former were single crystals of 99.95 pct purity which were leached approximately perpendicular to the "c" axis; they were supplied by the Gallard-Schlesinger Chemical Manufacturing Corp. The natural crystals, supplied by Minerals Unlimited, were transparent, analyzed 99.8 pct CaWO4, and in ultraviolet illumination exhibited the characteristic blue glow of substantially molybdenum-free scheelite. To permit exposure of an essentially constant surface area of scheelite to the leachant, the samples were mounted in Scotchcast Brand Resin No. 250 (Minnesota Mining and Manufacturing Co.). The mount-

Jan 1, 1970

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952

By J. W. Snavely

A practical mathematical treatment is presented for the determination and control of conveyor belt acceleration, particularly for conditions of starting where vertical curves are involved. A typical sample problem is analyzed, with required calculations, to clarify the procedure. THE part that acceleration plays in starting a belt conveyor and its effect on belt conveyor design are well understood in a general way. Its practical importance is easily overlooked, however, and under some conditions, it is absolutely necessary to give the problem of acceleration detailed study. Most handbooks on conveyor belting design adequately present basic data for the determination of acceleration values. This paper will only attempt to present practical thinking and a convenient method of treatment of acceleration in belt conveyor design. Mathematical Analysis In working out the various problems of conveyor belt acceleration, the starting point, as presented by the handbooks, is the familiar formula of "force of acceleration is equal to the mass times acceleration." By expressing these fundamental quantities in terms of belt conveyor design, it is possible to arrive at the unsuspected conclusion that the acceleration time for horizontal belt conveyors is independent of the load, and instead, dependent upon the belt speed, the type of drive arrangement and drive pulley, and the idler coefficient of friction. The mathematics leading to this conclusion are shown in Table I, which has been prepared to show this derivation. While at first the conclusion just given may not seem to be reasonable, further reflection indicates that obviously the type of drive pulley and the type of drive do affect materially the tension in the conveyor belt, and thus, as clearly shown, the time of acceleration is dependent upon the factors mentioned. Inasmuch as all of the factors except time are predetermined by the belt conveyor design, it becomes relatively easy to establish the accelerating time and to reduce further this time determination to a simple graph from which the time in seconds can be read directly. Such a graph is given in Fig. 1. The table appearing on Fig. 1 should be explained further. For a given belt speed, the time of acceleration can be expressed as a percentage of the belt speed. The time of acceleration is also dependent on the drive arrangement, and changes in the drive arrangement consequently change the time of acceleration. It further follows that for a given belt speed, the time expressed as a percentage of that belt speed also changes with the type of drive. Obviously then, it becomes possible to graph the percentage of speed for .each type of drive against the belt speed and accelerating time, after which, for a given belt speed and type of drive, the time can be read directly in seconds. Two constants were established for Fig. 1, the first one being the limiting of the maximum acceleration tension to 35 pct of the full load operating tension in the belt. The purpose of this is to limit the total tension imposed upon the belt during the acceleration period to 135 pct of the full load operating tension, 'which is the amount required to start or breakaway the fully loaded belt conveyor from rest. The other constant is the friction factor used for the idler equipment, which has been established as 0.022. For installations where it is necessary to establish the values of acceleration, invariably high grade idler equipment is used, and it has been established from field experience that 0.022 for the idler friction factor is amply conservative. The use of this friction factor for idlers must be tempered with judgment, of course, for occasions will arise where more power than indicated is required to start, even with the very best of equipment, such as low temperature operations that tend to congeal the grease in the bearings and thus produce additional friction drag. An inspection of the table in Fig. 1 affords a convenient rule of thumb method for determining the acceleration time, which conveniently can be 5 pct of the belt speed in seconds. The 5 pct of belt speed figure is close to the average for most types of drives. In using Fig. 1 it must be emphasized that it applies accurately to horizontal belt conveyors only.

Jan 1, 1953

By J. W. Snavely

A practical mathematical treatment is presented for the determination and control of conveyor belt acceleration, particularly for conditions of starting where vertical curves are involved. A typical sample problem is analyzed, with required calculations, to clarify the procedure. THE part that acceleration plays in starting a belt conveyor and its effect on belt conveyor design are well understood in a general way. Its practical importance is easily overlooked, however, and under some conditions, it is absolutely necessary to give the problem of acceleration detailed study. Most handbooks on conveyor belting design adequately present basic data for the determination of acceleration values. This paper will only attempt to present practical thinking and a convenient method of treatment of acceleration in belt conveyor design. Mathematical Analysis In working out the various problems of conveyor belt acceleration, the starting point, as presented by the handbooks, is the familiar formula of "force of acceleration is equal to the mass times acceleration." By expressing these fundamental quantities in terms of belt conveyor design, it is possible to arrive at the unsuspected conclusion that the acceleration time for horizontal belt conveyors is independent of the load, and instead, dependent upon the belt speed, the type of drive arrangement and drive pulley, and the idler coefficient of friction. The mathematics leading to this conclusion are shown in Table I, which has been prepared to show this derivation. While at first the conclusion just given may not seem to be reasonable, further reflection indicates that obviously the type of drive pulley and the type of drive do affect materially the tension in the conveyor belt, and thus, as clearly shown, the time of acceleration is dependent upon the factors mentioned. Inasmuch as all of the factors except time are predetermined by the belt conveyor design, it becomes relatively easy to establish the accelerating time and to reduce further this time determination to a simple graph from which the time in seconds can be read directly. Such a graph is given in Fig. 1. The table appearing on Fig. 1 should be explained further. For a given belt speed, the time of acceleration can be expressed as a percentage of the belt speed. The time of acceleration is also dependent on the drive arrangement, and changes in the drive arrangement consequently change the time of acceleration. It further follows that for a given belt speed, the time expressed as a percentage of that belt speed also changes with the type of drive. Obviously then, it becomes possible to graph the percentage of speed for .each type of drive against the belt speed and accelerating time, after which, for a given belt speed and type of drive, the time can be read directly in seconds. Two constants were established for Fig. 1, the first one being the limiting of the maximum acceleration tension to 35 pct of the full load operating tension in the belt. The purpose of this is to limit the total tension imposed upon the belt during the acceleration period to 135 pct of the full load operating tension, 'which is the amount required to start or breakaway the fully loaded belt conveyor from rest. The other constant is the friction factor used for the idler equipment, which has been established as 0.022. For installations where it is necessary to establish the values of acceleration, invariably high grade idler equipment is used, and it has been established from field experience that 0.022 for the idler friction factor is amply conservative. The use of this friction factor for idlers must be tempered with judgment, of course, for occasions will arise where more power than indicated is required to start, even with the very best of equipment, such as low temperature operations that tend to congeal the grease in the bearings and thus produce additional friction drag. An inspection of the table in Fig. 1 affords a convenient rule of thumb method for determining the acceleration time, which conveniently can be 5 pct of the belt speed in seconds. The 5 pct of belt speed figure is close to the average for most types of drives. In using Fig. 1 it must be emphasized that it applies accurately to horizontal belt conveyors only.

Jan 1, 1953

By J. E. Drury, W. M. Byers, E. J. Lynch

Measurements made with starch ~~~~s indicate that the Presence of starch serves to depress the streaming potential of a clay mud system. Measurements with pure starch slurries show that the addition of NaCl or CaO reduces the streaming potential significantly. The addition of NaOH, however, causes only a minor reduction in potential even when there are large changes in mud resistivity. INTRODUCTION In their excellent study of the streaming potential, Hill and Anderson' proposed that the presence of conductive solids within the filter medium will reduce the generated potential. This theory was demonstrated with measurements on shaly sandstone cores having various "b" factors; the cores with the higher negative b factors showed markedly lower potentials. (The factor b was originally defined by Hill and Milburn2 in an expression relating the resistivity of a shaly sandstone to the resistivity of the interstitial water: log F, = log F,, + b (log 100R,)'. 'he factor b, therefore, is a measure of the contribution of the conductive solids to the total conductivity of the sample. It has been found experimentally to be directly related to the amount of chemically exchangeable ion per unit pore volume.) In the logical extension of this hypothesis to the streaming potential created by filtration through mud cakes, they suggested that the presence of nonconductive starch in a drilling mud would have the opposite effect; i.e., it would cause the streaming POtential to be increased. The high streaming potentials that they observed with lime muds were attributed to this cause. A cross-plot of some of their results which are relevant to this discussion is given in Fig. 1. The lime-mud curves and untreated-mud curve are taken from curves given in their paper. The gyp-mud line was estimated from their statement that the measured streaming potential for gyp muds in the range of 1.5 to 2.0 ohm-m was approximately 18 mv/1,000 psi. These gyp-mud potentials were the lowest that they reported for any of the bentonitic-clay muds, and were the only ones which were less than the untreated-mud potentials. This very low streaming potential of gyp muds has also been observed in field studies.' By way of comparison, a U. of Texas publication4 gives the approxi-ate compositions for lime and gyp muds shown in Table 1. These materials are added to a bentonitic-clay mud base. It can be seen that both of these muds contain significant amounts of calcium salts and that the gyp mud has the higher concentration of starch. It would appear from this and from the data shown in Fig. 1 that starch may well be the cause of a streaming-potential reduction, rather than a potential increase. EXPERIMENTAL A series of streaming-potential experiments has been performed using a cell of a design similar to that reported by Wyllie.5 Calomel electrodes were used in both the mud slurry and the filtrate. Pressure in the cell was generated with high-pressure nitrogen. The primary objective of the investigation was to determine the effect of starch on the potential. Five different slurries were made which ranged in composition from untreated ben-tonitic mud (Baroid Aquagel) to a pure starch suspension (Baroid Im-permex). The intermediate slurries were prepared by mixing together a 9-lb/bbl clay mud with a 12-lb/bbl starch suspension in the ratios 1:3, 1:1 and 3:1. When starch was used alone, it was necessary to use an 18-Ib/bbl mixture, since leaner mixtures would not form a suitable filter cake. The clay mud used in the experiments was aged for three months before use. In addition to this series of measurements on the starch-clay mud mixtures, other experiments were performed to determine the effect on the potential of the absolute starch and Aquagel concentration, and the effect of adding various chemicals. RESULTS The effect of starch on the streaming potential is shown clcarly in Fig 2. Increasing percentages of starch resulted in n continually decreasing

By W. W. Stephen, J. P. Walsted, W. J. Kroll

FOR the production of carbides, various furnace types are available, especially those using arc, resistance, and high-frequency heating. Selection of a specific means of heating depends primarily on the material to be treated and the physical properties of the carbide produced. In the present case, zirconium carbide had to be prepared on an industrial scale as a raw material for the production of anhydrous zirconium chloride. Considering that a rather expensive pure oxide was to be used, the arc-furnace treatment recommended for zircon sands in a previous publication' was ruled out because of the considerable volatilization and dust losses caused by the blast of the arc. For this reason, either high-frequency or resistance heating seemed to offer more promise. Since there was not enough capacity of the former available, resistance heating was chosen. It was first thought that the Acheson silicon carbide furnace would be suitable for the present purpose, but the voltage in such a furnace, in which the current passes through the batch, varies from 220 to 75 v from the start to the end of a run. This variation is so great that a special tap transformer would have been required. Trouble was also expected by local melting of the carbide. Pure zirconium carbide melts at about 3527°C, but the melting point is brought down to 2427°C, according to Agte,2 when an excess of 6 pct C is present in the carbide. This we found confirmed by experiments in a high-frequency furnace. Excess carbon is needed in the batch to obtain a complete reduction. Fusion of the charge would cause great difficulties in an Acheson-type furnace because of the good electrical conductivity of the carbide as compared with that of the loose batch. Also, fused carbide is much more difficult to chlorinate than the spongy product that can be made in the radiation furnace described below. It was apparent that, to obtain a good-qual-ity zirconium carbide, the heat input would have to be well-controlled. The hairpin-resistor principle seemed to offer possibilities in this regard, and a furnace of this type was therefore developed. The advantages of the hairpin-resistor radiation principle have been discussed in previous publications, and a split-tube graphite-resistor furnace," now increasingly used in various laboratories, as well as a centrifugal quartz melting furnace4 of this type, has demonstrated the usefulness of this heating method. The hairpin-heater element has the following definite advantages over a straight resistor of the type used, for instance, by Georges:5 Its resistance is four times greater; it can expand freely; it is sturdier because of the larger diameter, and it has a larger radiation surface; there are no hot contacts that might wear out or overheat; only one clamp is used which permits assembling all electrical leads at one side of the furnace, making the other sides easily accessible to the operator. The shorter element and its larger diameter permit greater concentration of heat. The furnace developed is shown in fig. 1. The box (I), made of 2 1/2-in. graphite plates, has inside dimensions of 23x17x16 in. It contains the briquet-ted batch (2). The box is embedded in lampblack (3) up to the cover plate. The cover plate contains an opening for the gas escape (4) and for the observation hole (5), which permits measuring the temperature with an optical pyrometer. The cover plate is embedded in charcoal (6). The lampblack is contained in the insulating brick lining (7), held in the 1/4-in. sheet steel box (8). The graphite box is set on two rows of triangular graphite bars (9). The hairpin-heater element (10), the dimensions of which are given below the main drawing, extends horizontally in the graphite chamber and radiates freely on the batch. A graphite tube (11) keeps the lampblack from falling into the slot. The split electrode, which in reality is turned 90" against the drawing, is so arranged that the slot is vertical. The water-cooled packing gland (12) is insulated by an airgap from the heater element. A thin pipe (13)

Jan 1, 1951

By F. R. Morral, K. T. Aust

The preferred orientation and earing characteristics of ZS aluminum were studied. An empirical correlation was obtained relating earing behavior and variation of mechanical properties for face-centered cubic metals. Strain-ratio mecsurements for ZS were found to be in good agreement with Hill's theory of plastic anisotropy. DIRECTIONALITY in sheet metals may be revealed by earing in a cupping test, or by the variation of mechanical properties of tensile specimens taken at different angles to the rolling direction. However, no simple correlation appears to exist between earing and variation in mechanical properties in metals and alloys studied.1-5 Aluminum of commercial purity (known as 2S, with a specified minimum of 99.0 pct Al) cast by the direct casting process was chosen in the present investigation since ears at 45° or 0°, 90° can readily be obtained. Preferred orientation is often the principal cause of uneven metal flow, such as earing, and variation in mechanical properties. Consequently, the preferred orientation characteristics of 2s aluminum were initially studied using both X-ray diffraction and micrographic techniques. The variation of mechanical properties with angle to the rolling direction was next determined in an effort to clarify the apparent lack of correlation of earing behavior with mechanical properties for face-centered cubic metals. Strain-ratio*5,8 measurements were finally conducted to determine first, if the maximum values of the strain ratio occurred at the earing positions, and second, if Hill's theory of plastic anisotropy7 is applicable to other face-centered cubic metals such as aluminum. Detailed treatments, working, and heat treating are not given in this paper since this study is not concerned with the methods to produce earing, but to correlate earing with other properties and characteristics of the material. The percentage of earing was measured using the formula specified by the x—Y Aluminum Association, -------- X 100 = pct earing, where x is the height of the ear and y is the height of the valley from the bottom of the cup. Preferred Orientation Characteristics of 2S X-ray Studies: Beck and coworkers8 have determined that the rolling texture of 2s after 95 pct cold reduction may be approximately described by four equivalent ideal orientations near (123) [121]. Also, the recrystallization or annealing texture of 2s aluminum consists of four components of the (123) [l21] type, retained from the rolling texture, and of a (100) [001] or cube texture component." Fig. 1 illustrates the typical appearance of deep drawn earing cups with the corresponding X-ray diffraction patterns. The X-ray patterns were taken with copper radiation using the structure-integrating method'" in which the specimen is scanned during the X-ray exposure. The rolling direction was vertical and the rolling plane was perpendicular to the horizontal X-ray beam. It was found that an increase in the retained rolling texture component resulted in a greater 45" ear height, while an increase in the recrystallization texture component (i.e., cube texture) caused greater 0°, 90° earing. X-ray diffraction studies of 2s cold rolled to final thickness followed by a final anneal have shown that the rolling texture, and also the retained component of the rolling texture after annealing, are increased with greater cold-rolling reduction. The preferred orientation characteristics of 2s sheets given an intermediate anneal between cold rolling followed by a final anneal were found to depend on the position of the intermediate anneal during cold rolling. For instance, three identical samples of 2s homogenized ingot, each 1 in. thick, were given the following cold-rolling and annealing treatments: 1—50 pct reduction, intermediate anneal, 96 pct reduction to 0.020 in. and a final anneal; 2—75 pct reduction, intermediate anneal, 92 pct reduction to 0.020 in. and a final anneal; and 3—90 pct reduction, intermediate anneal, 80 pct reduction to 0.020 in. and a final anneal. The intermediate and final annealing treatments consisted of a 70°F per hr heating rate, held 6 hr at 800°F and air cooled. Typical X-ray patterns after each of these treatments are shown in Fig. 2. It was evident that after treatment 1, the retained rolling texture component predominated; after treatment 2, the retained roll-

Jan 1, 1954

By J. Washburn, R. Drouard, E. R. Parker

Temperature dependence of the rate of recovery in zinc single crystals after a simple shear deformation at low temperature was investigated. Some tentative suggestions regarding the annealed and strain-hardened states of a crystal are discussed. RECOVERY may be defined as the gradual return of the mechanical and physical properties of strain-hardened metal to those characteristic of the annealed material; an increase in temperature increases the rate of recovery. The annealing process in strain-hardened polycrystalline metals is complicated by the inhomogeneity of strain which always exists in aggregates. Polygonization in bent regions of the crystals and growth of new almost strain-free grains starting at points of severe local distortion1-:' make it almost impossible to isolate and study the recovery process. Homogeneously strained single crystals, however, do not polygonize or re-crystallize and hence they can be used advantageously to study recovery. In such crystals strain hardening is completely removed by recovery alone. Since recovery is a process whereby certain lattice disturbances introduced by plastic flow are gradually reduced, a knowledge of the rate and temperature dependence of this process for various conditions of prestrain might be helpful in formulating a model of the strain-hardened state. For simplicity it seemed desirable to limit the type of prestrain to the simplest obtainable, i.e., simple shear strain. In the experiments to be described, recovery was studied by observing changes in the stress-strain curve of prestrained zinc single crystals held for various times at temperatures above that employed for straining. Single crystals were grown from the melt by a modified Bridgeman technique from Horse Head Special zinc 99.99 pct pure, and from spectrographically pure zinc 99.999 pct pure. They were grown as 1 in. diameter spheres and acid-machined' to the final specimen contour. The test section was a cylinder about 1/8 in. high and 3/4 in. in diameter. The conical sections adjacent to the test section were cemented into the grips so the load could be transmitted to the crystal as uniformly as possible. The specimens were oriented so that in testing the maximum shear stress was applied along one of the slip directions, [2110], in the (0001) plane. Details of the production and testing of such specimens have been presented.' Each test was carried out according to the following schedule: 1—The crystal was strained at — 50°C until it reached a maximum shear stress, ,,,. The strain rate was approximately 5 pct per min in all cases. 2—After straining, the crystal was unloaded before the temperature was changed. Unloading required about 3 min. 3—The temperature of the specimen was then increased from — 50°C to the temperature, T, of recovery. This change in temperature was completed in a time of less than 2 min. The specimen remained at temperature, T, for a time, t, which differed for the various specimens. 4—Thereafter the temperature was again reduced to — 50 °C in approximately 3 min. 5—While at —50°C, the stress-strain curve after recovery was obtained. 6—The specimen was then unloaded and annealed for 1 hr at 375 °C in a helium atmosphere to bring about complete recovery. Cooling to room temperature after anneal required 90 min. 7—The same crystal could be re-used for another test because the plastic properties after annealing closely duplicated those of the original crystal. The specimen was immersed during the test in a bath of methyl alcohol which, through a system of tubes, could be pumped through either of two heat exchangers to regulate the temperature; this was accomplished by circulating the liquid through coils immersed in a bath of acetone and dry ice for cooling or in a bath of warm water for heating. Test temperatures were thus maintained constant within ±1°C. The — 50°C temperature was low enough so that no measurable recovery occurred during unloading and reloading. The stress-strain curve continued after recovery along a path below, but approximately parallel to, the path of a curve obtained in an uninterrupted test. Fig. 1 shows some of the results from a specimen of 99.999 pct Zn. The amount of downward displacement of the curve due to recovery was a

Jan 1, 1954

By Herbert Hoover

THE Federation of Engineering Societies has been created for the sole purpose of public service. This initial meeting surely warrants some discussion of a few of the problems to which this organization, for expression of the --. engineering mind, can quite well give consideration. Some of the greatest of the problems before the country and, in fact, before the world, are those growing out of our industrial development. The enormous industrial expansion of the last fifty' years has lifted the standard of living and comfort beyond any dream of our forefathers. Our economic system under which it has been accomplished has given stimulation to invention, to enterprise, to individual improvement of the highest order, yet it presents a series of human and social difficulties for the solution of which we are groping. The congestion of population is producing subnormal conditions of life. The vast repetitive operations are dulling the human mind. The intermittency bf employment due to the bad coordination of industry, the great waves of unemployment in the ebb and flow of economic tides, produce infinite wastes and great suffering. Our business enterprises have become so large and complex that the old personal relationship between employer and worker has to a great extent disappeared. The aggregation of great wealth, with its power of economic domination, presents social, economic ills which we are constantly struggling to remedy.

Jan 1, 1920

By S. F. Bartram, G. A. Chase

COMPUTED X-ray diffraction powder patterns of YNi3, YNi5, and CbBe3 are available on request from either author.

Jan 1, 1968

By P. R. Sahm, T. V. Pruss

Mixtures of fine GaSb and Gds as well as preal-loyed GaSbl,As, powders were hot-pressed at 690°C and 25,000 psi. Dense alloys with compositional gradients of less than 5 pct were obtained from mixtures containing about 20 mol pct GaAs. For x < 0.2, there were increasing compositional gradients, and for x > 0.2 a GaAs-rich second phase appeared in the microstructure. Densification as well as alloying wlechanisms were enhanced by dissociation and, possibly, oxidation reactions of the powders. Densification of coarse prealloyed material, however, primarily depended on plastic flow phenomena and required temperatures just below solidus and pressures of 50,000 psi Thermal and electrical properties were measured. Although in no case was the figure of merit of melt growth materials approached closer than to within 25 pct, the better overall thermoelectric properties were found in coarse-grained, prealloyed materzals which had been compacted to near theoretical density and where grain regrowth had been induced. Similar results are believed to hold in other binary 111-V compound systems if processed under similar conditions. The densification of unalloyed GaSb powders during pressure sintering (= hot pressing) was shown to depend strongly on powder particle size.&apos; Fine powders displayed a "liquid skin effect" that enhanced compaction through the presence of liquid gallium, whereas coarse powders compacted predominantly by plastic flow. The liquid skin effect, in particular, appeared attractive for alloying GaSb with other, higher-melting, III-V compounds, and to densify these in a one-step operation. This is of special interest in the case of III-V compound alloys as the conventional techniques of melt growth or long-time annealing of powders2 is very time-consuming, especially in cases where a large separation of liquidus and solidus can be expected, such as in GaSbl alloys.2 It was felt that experimentation with this system, a particularly unfavorable example, would allow us to extrapolate to several other, more favorable, cases. Uses of Ill-V alloys are most evident in thermoelectric energy conversion devices.&apos; For this reason certain thermal and electrical properties were measured and compared to those of melt-grown material and to hot-pressed prealloyed powders. EXPERIMENTAL PROCEDURE The pressure-sintering apparatus has been previously described.&apos; Using this equipment, both powder mixtures of GaSb with GaAs and prealloyed GaSbl-,As, powders were hot-pressed. The mixtures were pre- pared from cast GaSb and melt-grown GaAs. The prealloyed material was obtained from stoichiometric melts, initially heated to 1200°C in an evacuated quartz ampoule, and then annealed in the solidus-liquidus interval. A typical annealing cycle consisted of a heating to 850°C (1 hr), extended successive annealing at 750°C (65 hr), and slow stepwise cooling (25 hr) to below solidus. The GaSb, GaAs, and GaSbl-,As, materials were ground in a vibrational mill to particle sizes below 500 . A jet mill reduced these further where necessary. Fine powders were analyzed by Coulter counting for their size distribution. Average sizes by volume were calculated from the data. Mixing of the powders, where necessary, was carried out through rapid vibrational motion. The hot-pressing operation consisted of a degassing period of 15 hr, in most cases at 690°C, followed by several hours of compression, normally 25,000 psi at 690°C for powder mixtures and 50,000 psi at 710°C for prealloyed powders. The chemical compositions were confirmed by X-ray fluorescence analysis. To estimate the degree of solid solution achieved, lattice parameters were determined and interpreted according to Vegard&apos;s rule. In addition, optical microscopy helped to correlate the relative amounts of the phases present as well as the degree of porosity to the measured density. To reveal grain boundaries, polished surfaces were etched4 with H 2 O:H 2 O:HCl = 2:l:l. In several cases microscopic concentration gradients were monitored by electron-probe analysis-. RESULTS AND DISCUSSION Alloying and Densification of GaSn-GaAs Powder Mixtures. After preliminary experiments showed that no appreciable alloying took place in mixtures of coarse GaSb (22.5 p) and fine GaAs (2.5 p) powders, hot pressing of mixtures was confined to fine powders only (3.1 and 2.4 p, respectively). Alloying and densification apparently occurred simultaneously with a grain regrowth mechanism which depended on the presence of a liquid phase.&apos; The liquid phase was provided by the dissociation of GasbS particles into liquid gallium and antimony above 555°C. This not only enhanced grain regrowth and densification, as in unalloyed GaSb,&apos; but took on additional importance here for the alloying process. Alloying was speeded up by the resulting liquid-solid interaction as compared to the very slow solid-state diffusion process normally expected at these temperatures.&apos; The results obtained with a series of powder mixtures have been compiled in Table I. It is seen that for mixtures with less than 20 mol pct GaAs, x < 0.2, the compositional ranges increased and for x > 0.2 a GaAs-rich phase and free antimony appeared in the microstructure in sizable amounts.

Jan 1, 1968